Agrochemical formulations for water surface application

Abstract

New agrochemical formulations for application to the water of paddy fields, which formulations comprise A) at least one solid core material having an apparent specific density of less than 1 and a particle diameter within the range from about 300 μm to about 1,400 μm, and B) a coating layer comprising at least one biologically active compound, at least one substance having the ability to reduce the interfacial tension between water and air, at least one oily substance and, if appropriate, one or more additives, and the use of such agrochemical formulations for applying biologically active compounds to the water of paddy fields.

We claim: 
     
       1. An agrochemical formulation in the form of solid particles consisting essentially of A) at least one solid core material having an apparent specific density of less than 1 and a particle diameter within the range from about 500 μm to about 1,400 μm, wherein the core material is selected from the group consisting of pumice, calcined perlite, processed shirasu, calcined obsidian, calcined pumice and vermiculite, and   B) a coating layer comprising at least one biologically active compound,   at least one substance having the ability to reduce the interfacial tension between water and air selected from the group consisting of alkylbenzenesulfonates, alkylsulfates, alkylnaphthalenesulfonates, alkylphosphoric esters, polyoxyethylene alkyl ethers, glycerin fatty acid esters, sorbitan fatty acid esters, dialkylsulfosuccinates, ligninsulfonate, condensates of naphthalenesulfonate and formalin, alkylammonium salts, alkylglycine salts, alanine salts, siliconpolyether surfactants, alkylallylsulfonate and a camphor, and spindle oil.     
     
     
       2. An agrochemical formulation according to claim 1, wherein the biologically active compound is selected from the group consisting of insecticidal compounds, fungicidal compounds, nematocidal compounds, herbicidal compounds, plant nutritive substances and plant growth regulants. 
     
     
       3. An agrochemical formulation according to claim 1 comprising at least one additive selected from extenders, stabilizers and colorants. 
     
     
       4. An agrochemical formulation according to claim 1, wherein said biologically active compound is a herbicidal compound. 
     
     
       5. An agrochemical formulation according to claim 1, wherein said biologically active compound is at least one compound selected from the group consisting of 2-benzothiazol-2-yloxy-N-methylacetanilide,   2-isopropoxyphenyl-N-methylcarbamate,   1-(6-chloro-3-pyridylmethyl)-N-nitro-imidazolidin-2-ylideneamine,   O,O-dimethyl-O- 3-methyl-4-(methylthio)-phenyl!-thiophosphate,   1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone,   all-rac-1-(biphenyl-4-yloxy)-3,3-dimethyl-1- (1H- 1,2,4-triazol- 1-yl)-butan-2-ol,   zinc propylenebisdithiocarbamate,   (RS)-2-bromo-N-(α,α-dimethylbenzyl)-3,3-dimethyl-butyramide,   2-chloro-2',6'-diethyl-N-(2-propoxyethyl)- acetanilide,   2-chloro-2',6'-diethyl-N-(2-butoxymethyl)- acetanilide,   2-chloro-N-(3-methoxy-2-thenyl)-2',6'- dimethylacetanilide,   S-(4-chlorobenzyl)-N,N-diethylthiocarbamate,   S-benzyl 1,2-dimethylpropyl(ethyl)thio-carbamate,   O-3-tert-butylphenyl 6-methoxy-2-pyridyl- (methyl)thiocarbamate,   S-ethylhexamido-1H-azepin-1-carbothioate,   1-(diethylcarbamoyl)-3-(2,4,6-trimethyl-phenyl- sulfonyl)-1,2,4-thiazole,   1-(3-chloro-4-trifluoromethylphenyl)-4-(N,N-dimethylcarbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-trifluoromethylthio-phenyl)-4-(N,N-dipropyl carbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-trifluoromethoxy-phenyl)-4-(N,N-dipropylcarbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-isopropylphenyl)-4-(N,N-diethyl- carbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-isopropylphenyl)-4-(N,N-dipropylcarbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-isopropylphenyl)-4-(N,N-diallyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N,N-dipropylcarbamoyl)-5(4H)-tetrazolinone,   1-(2-chloro-6-methylphenyl)-4-(N,N-diethyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2,6-dichlorophenyl)-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone,   1-(2-chloro-6-methylphenyl)-4-(N-ethyl-N-iso-propyl)-5(4H)-tetrazolinone,   1-(2-chloro-6-methylphenyl)-4-(N,N-dipropyl-carbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N-cyclopentyl-N-ethyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N-cyclopentyl-N-propyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N-cyclohexyl-N-ethyl-carbamoyl)-5(4H)-tetrazolinone,   1-(2-chloro-6-methylphenyl)-4-(N-cyclopentyl-N-propylcarbamoyl)-5(4H)-tetrazolinone,   1-(2-bromophenyl)-4-(N-cyclopentyl-N-ethyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-bromophenyl)-4-(N-cyclopentyl-N-propyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-bromo-6-methylphenyl)-4-(N-cyclopentyl-N-propylcarbamoyl)-5(4H)-tetrazolinone,   methyl 2- (4,6-dimethoxy-2-pyrimidinyl)-oxy!- 6- 1-(methoxyimino)-ethyl!-benzoate,   methyl α-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-O-toluate,   ethyl-5-(4,6-dimethoxypyrimidin-2-yl-carbamoyl sulfamoyl)- 1-methylpyrazol-4-carboxylate,   N-(2-chloroimidazol  1,2-a!pyridin-3-yl-sulfonyl)-N'-(4,6-dimethoxy-2-pyrimidyl)urea,   N-((4,6-dimethoxypyrimi din-2-yl)-aminocarbonyl)- 1-methyl-4-(2-methyl-2H-tetrazol-5-yl)-1H-pyrazol-5-sulfonamide,   N-  4,6-dimethoxy-1,3,5-triazin-2-yl)-amino!-carbonyl!-2-(2-methoxyethoxy)benzenesulfonamide,   1-  o-(cyclopropylcarbonyl)phenyl!-sulfamoyl-3-(4,6-dimethoxy-2-pyrimidinyl)urea,   4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5- yl-p-toluenesulfonate,   2- 4-(2,4-dichloro-m-toluyl)-1,3-dimethyl-pyrazol-5-yloxy!-4-methylacetophenone,   2- 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yloxy!-acetophenone,   2-(β-naphthyloxy)-propionanilide,   (RS)-2-(2,4-dichloro-m-tolyloxy)-propion-anilide,   n-butyl (R)-2- 4-(2-fluoro-4-cyanophenoxy)- phenoxy!-propionate,   1-(α,α-dimethylbenzyl)-3-p-tolylurea,   N- (2-chlorophenyl)-methyl!-N'-(1-methyl-1- phenylethyl)-urea,   2-methyl-4-chlorophenoxybutyric acid,   2,4-dichlorophenoxyacetic acid,   2,4-bis-(ethylamino)-6-methylthio-1,3,5-triazine,   2-ethyl amino-4-(1,2-dimethylpropylamino)-6- methylthio-1,3,5-triazine.   
     
     
       6. An agrochemical formulation according to claim 1, wherein said biologically active compound is at least one of 2-benzothiazol-2-yloxy-N-methylacetanilide or 1-(2-chloro-phenyl)-4-(N-cyclohexyl-N-ethylcarbamoyl)-5(4H)-tetrazolinone. 
     
     
       7. A method for applying agrochemicals to the water of paddy fields, which method comprises adding to the water surface of paddy fields a formulation in the form of solid particles consisting essentially of A) at least one solid core material having an apparent specific density of less than 1 and a particle diameter within the range from about 500 μm to about 1,400 μm, wherein the core material is selected from the group consisting of pumice, calcined perlite, processed shirasu, calcined obsidian, calcined pumice and vermiculite, and   B) a coating layer comprising at least one biologically active compound,   at least one substance having the ability to reduce the interfacial tension between water and air selected from the group consisting of alkylbenzenesulfonates, alkylsulfates, alkylnaphthalenesulfonates, alkylphosphoric esters, polyoxyethylene alkyl ethers, glycerin fatty acid esters, sorbitan fatty acid esters, dialkylsulfosuccinates, ligninsulfonate, condensates of naphthalenesulfonate and formalin, alkylammonium salts, alkylglycine salts, alanine salts, siliconpolyether surfactants, alkylallylsufonates and a camphor, and spindle oil.     
     
     
       8. A method according to claim 7, wherein the biologically active compound is selected from the group consisting of insecticidal compounds, fungicidal compounds, nematocidal compounds, herbicidal compounds, plant nutritive substances and plant growth regulantes. 
     
     
       9. A method according to claim 7, wherein said biologically active compound is a herbicidal compound. 
     
     
       10. A method according to claim 7, comprising at least one additive selected from extenders, stabilizers and colorants. 
     
     
       11. A method according to claim 7, wherein said biologically active compound is at least one compound selected from the group consisting of 2-benzothiazol-2-yloxy-N-methylacetanilide,   2-isopropoxyphenyl-N-methylcarbamate,   1-(6-chloro-3-pyridylmethyl)-N-nitro-imidazolidin-2-ylideneamine,   O,O-dimethyl-O- 3-methyl-4-(methylthio)-phenyl!-thiophosphate,   1-(4-chlorophenoxy)-3,3-dimethyl- 1-(1,2,4- triazol-1-yl)-2-butanone,   all-rac- 1-(biphenyl-4-yloxy)-3,3-dimethyl-1-(1H-1,2,4-triazol- 1-yl)-butan-2-ol,   zinc propylenebisdithiocarbamate,   (RS)-2-bromo-N-(α,α-dimethylbenzyl)3,3- dimethyl-butyramide,   2-chloro-2',6'-diethyl-N-(2-propoxyethyl)- acetanilide,   2-chloro-2',6'-diethyl-N-(2-butoxymethyl)- acetanilide,   2-chloro-N-(3-methoxy-2-thenyl)-2',6'- dimethylacetanilide,   S-(4-chlorobenzyl)-N,N-diethylthiocarbamate,   S-benzyl 1,2-dimethylpropyl(ethyl)thio-carbamate,   O-3-tert-butylphenyl 6-methoxy-2-pyridyl-(methyl)thiocarbamate,   S-ethylhexamido-1H-azepin- 1-carbothioate,   1-(diethylcarbamoyl)-3-(2,4,6-trimethyl-phenyl-sulfonyl)-1,2,4-thiazole,   1-(3-chloro-4-trifluoromethylphenyl)-4-(N,N-dimethylcarbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-tri fluoromethylthio-phenyl)-4-(N,N-dipropylcarbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-trifluoromethoxy-phenyl)-4-(N,N-dipropylcarbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-isopropylphenyl)-4-(N,N-diethyl- carbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-isopropylphenyl)-4-(N,N-dipropylcarbamoyl)-5(4H)-tetrazolinone,   1-(3-chloro-4-isopropylphenyl)-4-(N,N-diallyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N,N-dipropylcarbamoyl)-5(4H)-tetrazolinone,   1-(2-chloro-6-methylphenyl)-4-(N,N-diethyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2,6-dichlorophenyl)-4-(N,N-diethylcarbamoyl)-5(4H)-tetrazolinone,   1-(2-chloro-6-methylphenyl)-4-(N-ethyl-N-iso-propyl)-5(4H)-tetrazolinone,   1-(2-chloro-6-methylphenyl)-4-(N,N-dipropyl-carbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N-cyclopentyl-N-ethyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N-cyclopentyl-N-propyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-chlorophenyl)-4-(N-cyclohexyl-N-ethyl-carbamoyl)-5(4H)-tetrazolinone,   1-(2-chloro-6-methylphenyl)-4-(N-cyclopentyl-N-propylcarbamoyl)-5(4H)-tetrazolinone,   1-(2-bromophenyl)-4-(N-cyclopentyl-N-ethyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-bromophenyl)-4-(N-cyclopentyl-N-propyl- carbamoyl)-5(4H)-tetrazolinone,   1-(2-bromo-6-methylphenyl)-4-(N-cyclopentyl-N-propylcarbamoyl)-5(4H)tetrazolinone,   methyl 2- (4,6-dimethoxy-2-pyrimidinyl)-oxy!- 6- 1-(methoxyimino)-ethyl!-benzoate,   methyl α-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-O-toluate,   ethyl-5-(4,6-dimethoxypyrimidin-2-yl-carbamoylsulfamoyl)- 1-methylpyrazol-4-carboxylate,   N-(2-chloroimidazol  1,2-a!pyridin-3-yl-sulfonyl)-N'-(4,6-dim ethoxy-2-pyrimidyl)urea,   N-((4,6-dimethoxypyrimi din-2-yl)-aminocarbonyl)-1-methyl-4-(2-methyl -2H-tetrazol-5-yl)--1H-pyrazol-5-sulfonamide,   N-  4,6-dimethoxy-1,3,5-triazin-2-yl)-amino!-carbonyl!-2-(2-methoxyethoxy)benzenesulfonamide,   1-  o-(cyclopropylcarbonyl)phenyl!-sulfamoyl-3-(4,6-dimethoxy-2-pyrimidinyl)urea,   4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl-p-toluenesulfonate,   2- 4-(2,4-dichloro-m-toluyl)-1,3-dimethyl-pyrazol-5-yloxy!-4-methylacetophenone,   2- 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yloxy!-acetophenone,   2-(β-naphthyloxy)-propionanilide,   (RS)-2-(2,4-dichloro-m-tolyloxy)-propion-anilide,   n-butyl (R)-2- 4-(2-fluoro-4-cyanophenoxy)- phenoxy!-propionate,   1-(α,α-dimethylbenzyl)-3-p-tolylurea,   N- (2-chlorophenyl)-methyl!-N'-(1-methyl-1- phenylethyl)-urea,   2-methyl-4-chlorophenoxybutyric acid,   2,4-dichlorophenoxyacetic acid,   2,4-bis-(ethylamino)-6-methylthio-1,3,5-triazine,   2-ethyl amino-4-(1,2-dimethylpropylamino)-6- methylthio-1,3,5-triazine.   
     
     
       12. A method according to claim 7, wherein said biologically active compound is at least one of 2-benzothiazol-2-yloxy-N-methylacetanilide or 1-(2-chloro-phenyl)4-(Ncyclohexyl-N-ethylcarbamoyl)-5(4H)-tetrazolinone.